WO2007110532A2

WO2007110532A2 - Dyeing composition containing a thiol/disulphide fluorescent colorant comprising a heterocycle, with an external cationic charge, and method for lightening keratin materials using said colorant

Info

Publication number: WO2007110532A2
Application number: PCT/FR2007/050998
Authority: WO
Inventors: Andrew Greaves; Nicolas Daubresse
Original assignee: L'oréal
Priority date: 2006-03-24
Filing date: 2007-03-23
Publication date: 2007-10-04
Also published as: EP2004754B1; JP5254950B2; JP2009533488A; WO2007110532A3; EP2004754A2

Abstract

The invention relates to a dyeing composition comprising a heterocyclic thiol/disulphide fluorescent colorant, and to a method for colouring keratin materials, especially keratin fibres, particularly human keratin fibres such as hair, with a lightening effect, using said composition. The invention also relates to novel heterocyclic thiol/disulphide fluorescent colorants and the uses thereof for lightening keratin materials. Said composition produces a lightening effect which is especially tenacious and visible on dark keratin fibres.

Description

DYE COMPOSITION COMPRISING A FLUORESCENT COLOR

THIOL / DISULFIDE HETEROCYCLE AND EXTERNAL CATIONIC LOAD,

METHOD FOR LIGHTENING KERATINIC MATERIALS FROM

THIS COLOR

The invention relates to the dyeing of keratin materials using fluorescent thiol / disulfide dyes comprising a heterocycloalkyl group.

It is known to dye keratinous fibers, especially human fibers, by direct dyeing. The method conventionally used in direct dyeing consists in applying to the keratin fibers direct dyes which are colored and dyeing molecules having an affinity for the fibers, allowing them to diffuse and then rinsing the fibers.

The direct dyes which are conventionally used are, for example, dyes of the nitrobenzene type, anthraquinone dyes, nitropyridines, dyes of the azo, xanthene, acridine, azine or triarylmethane type.

The colorings that result from the use of direct dyes are temporary or semi-permanent dyes because the nature of the interactions that bind the direct dyes to the keratinous fiber, and their desorption of the surface and / or the core of the fiber are responsible their low dyeing power and their poor resistance to washes or perspiration.

Furthermore, the coloration of keratinous fibers from conventional direct dyes does not make it possible to significantly lighten the keratin fibers.

The lightening of the color of keratinous fibers, more particularly dark to lighter shades, possibly modifying the shade of these, constitutes an important demand.

Conventionally, to obtain a lighter coloration is implemented a chemical bleaching process. This method consists in treating keratin materials such as keratinous fibers, in particular the hair, by a strong oxidizing system, generally consisting of hydrogen peroxide associated or not with persalts, most often in an alkaline medium.

This bleaching system has the drawback of degrading keratin materials, in particular keratinous fibers, especially human fibers such as the hair, and of altering their cosmetic properties. Fibers indeed tend to become rough, more difficult to disentangle and more fragile. Finally, the lightening or the bleaching of keratinous fibers by oxidizing agents is incompatible with the treatments for modifying the shape of said fibers, particularly in the straightening treatments. Another lightening technique consists in applying fluorescent direct dyes to dark hair. This technique described in particular in the documents FR 2830189 and WO 2004/091473 makes it possible to respect the quality of the keratinous fiber during the treatment, but the fluorescent dyes employed do not exhibit satisfactory resistance to shampooing. To increase the tenacity of the direct dyes, it is known to fix direct dyes by covalent bonding to the hair. For example, it is known to react dyes with reactive groups with the residues of cystine or cysteine very numerous in keratinous fibers see for example Journal of the Society of Dyers and Colourists, Guise and Stapleton, 9_1, 259-264 ( 1975); Journal of Cosmetic Chemistry, 42, 1-17 (1991); CA 2024509.

In addition, it is known to protect the thiol function or functions contained in a molecule to be grafted to the hair before being applied to said hair WO 99/51 194. However, this application does not mention the use of fluorescent dyes which make it possible to color or thinning hair. Other disulfide dyes known for dyeing keratinous fibers are disulfide derivatives of aminothiophenol derivatives. Such dyes are described, for example, in patent FR 1 156407. These dyes may be used under relatively mild conditions, in the presence of a slightly reducing medium or after a reducing pretreatment of the hair. However, these dyes may cause color turns during application.

Finally, the document WO 2005/097051 describes disulfide aza-imidazolium dyes for the direct dyeing of keratin fibers.

The object of the present invention is to provide novel systems for dyeing keratin materials, in particular human keratinous fibers, in particular the hair, which do not have the drawbacks of existing bleaching processes. In particular, one of the aims of the present invention is to provide direct dyeing systems which make it possible to obtain lightening effects, in particular on naturally or artificially dark keratin fibers, which are stubborn in the face of successive shampoos, which do not degrade the fibers. keratinous and which do not alter their cosmetic properties.

This object is achieved with the present invention which relates to a process for dyeing keratin materials, in particular keratinous fibers, in particular human fibers such as the hair, more particularly the dark hair, consisting in applying to the keratin materials a dye composition. comprising, in a suitable cosmetic medium, at least one fluorescent dye with a heterocyclic group chosen from the following dyes of formula (I), (II) or (III):

their organic or inorganic acid salts, optical isomers, geometric isomers, and solvates such as hydrates; formulas (I), (II) or (III) in which: R _a and R ' _a , which are identical or different, represent an aryl (C 1 -C ₄ ) alkyl group or a (C ₁ -C ₆ ) alkyl group optionally substituted with a hydroxyl or amino (C ₁ -C ₄ ) alkylamino (C ₁ -C ₄ ) group; dialkylamino, said alkyl radicals being able to form with the nitrogen atom which carries them a 5- to 7-membered heterocyl, optionally comprising another heteroatom different or different from nitrogen; preferably R ₃ and R ' _a represent a (C ₁ -C ₃ ) alkyl group optionally substituted by a hydroxyl group such as methyl or ethyl, or a benzyl group;

> R ' _C represents a hydrogen atom, an aryl (CrC ₄ ) alkyl group, an optionally substituted C ₁ -C ₆ alkyl group;

> R _g, R _'g, R _"g, R" _g, R _h, R' _h, R _"h and R"_'h, identical or different, represent a hydrogen atom, a halogen atom, an amino, (C ₁ -C ₄ ) alkylamino, (C ₁ -C ₄ ) dialkylamino, cyano, carboxy, hydroxy, trifluoromethyl, acylamino, C ₁ -C ₄ alkoxy, (poly) hydroxyalkoxy C ₂ - C ₄ , alkylcarbonyloxyalkoxycarbonyl, alkylcarbonylamino, an acylamino, carbamoyl, alkylsulphonylamino radical, an amino-sulphonyl radical, or a (C ₁ -C ₄ ) alkyl radical optionally substituted with a group chosen from (C ₁ -C ₄ ) alkoxy, hydroxy , cyano, carboxy, amino, (C ₁ -C ₄ ) alkylamino and (C ₁ -C ₄ ) dialkylamino, or the two alkyl radicals carried by the nitrogen atom of the amino group form a heterocycle comprising from 5 to 7 linkages and optionally comprising another heteroatom identical to or different from that of the nitrogen atom; particularly R _9, R _'g, R _"g, R" _g, R _h, R' _h, R _"h and R"_'h is a hydrogen atom;

or two groups R ₉ and R '_g; R " _g and R '"_g; R _h and R '_h; R " _h and R '" _h borne by two adjacent carbon atoms together form a benzo, indeno ring, a fused heterocycloalkyl or fused heteroaryl group; the benzo, indeno, heterocycloalkyl or heteroaryl ring being optionally substituted by a halogen atom, an amino group, (C ₁ -C ₄ ) alkylamino, (C ₁ -C ₄ ) dialkylamino, cyano, carboxy, hydroxy, trifluoromethyl, a acylamino, alkoxy, C ₁ -C ₄ (poly) hydroxyalkoxy, C ₂ -C ₄ alkoxycarbonyl alkylcarbonyloxy, alkylcarbonylamino, acylamino, carbamoyl, alkylsulfonylamino, amino-sulfonyl group, or a (C ₁ -C ₄ ) alkyl optionally substituted with: a group chosen from (C ₁ -C ₄ ) alkoxy, hydroxy, cyano, carboxy, amino, (C ₁ -C ₄ ) alkylamino, (C ₁ -C ₄ ) dialkylamino, or both radicals alkyl borne on the nitrogen atom of the amino group form a 5- to 7-membered heterocyclic ring and optionally comprising another heteroatom identical to or different from that of the nitrogen atom; particularly R ₉ and R '_g; R " _g and R '" _g together form a benzo group;

> R ,, R ',; R ", and R"", which may be identical or different, represent a hydrogen atom or a (C ₁ -C ₄ ) alkyl group; especially R ,, R ',; R "and R""represent a hydrogen atom;

> R 1, R ₂ , R 3, R ₄ , R ' ₁ , R' ₂ , R ' ₃ and R' ₄ , which may be identical or different, represent a hydrogen atom or a (C ₁ -C ₄ ) alkyl group (C ₁ -C ₄ ) alkoxy, hydroxy, cyano, carboxy, amino, (C ₁ -C ₄ ) alkylamino, (C ₁ -C ₄ ) dialkylamino, said alkyl radicals being able to form with the nitrogen atom which carry, a 5- to 7-membered heterocyl, optionally comprising another heteroatom different or different from nitrogen; in particular R ₁ , R ₂ , R 3, R ₄ , R '1, R' ₂ , R ' ₃ and R' ₄ are hydrogen atoms or an amino group; in particular R ₁ , R ₂ , R ₃ and R ₄ represent a hydrogen atom; > T _a or T _b , identical or different represent: i) a covalent bond σ, ii) or one or more radicals or combinations thereof selected from -SO ₂ -,

-O-, -S-, -N (R) -, -N ⁺ (R) (R ⁰ ) -, -C (O) -, with R and R °, identical or different, representing a hydrogen atom , alkyl radical C ₁ -C ₄ hydroxyalkyl, C ₁ -C ₄ or a aryKd ^ Jalkyle; in particular, T ₃ and T _b represent a covalent bond σ or a group chosen from -N (R) -, -C (O) -, -C (O) -

N (R) -, -N (R) -C (O) -, -C (O) -N (R) -C (O) -, -O-C (O) -, -C (O) - O- and

-N ⁺ (R) (R ⁰ ) -, with R, R ° identical or different representing a hydrogen atom, a C ₁ -C ₄ alkyl group; in particular, T ₃ and T _b represent a bond σ; iii) a heterocycloalkyl or heteroaryl radical, cationic or non-cationic, preferably monocyclic, containing one or two heteroatoms, particularly two nitrogen atoms, and especially comprising from 5 to 7 members such as imidazolium, piperazinyl, piperazinium, homopiperazinyl; homopiperazinium optionally substituted with a (C ₁ -C ₄ ) alkyl group such as methyl;

^/ V ^. _M ^ ^N - - TV ^. _M M ', identical or different, represent a grouping

I 'I cationic or non-cationic heterocyclic, optionally substituted; in particular the heterocycle is monocyclic, saturated, and comprises in total one to two nitrogen atoms and 5 to 8 members;

> m, m ', n and n', which are identical or different, represent an integer between 0 and 6 with m + n and m '+ n', which may be identical or different, represent an integer between 1 and 10 inclusive; especially the sum m + n = m '+ n' is an integer inclusive between 2 and 4; preferentially when T ₃ and T _b represent a covalent bond σ, m + n = m '+ n' is an integer equal to 2; > M 'representing an anionic counterion; and

Y represents: i) a hydrogen atom; ii) an alkali metal; iii) an alkaline earth metal; iv) an ammonium group: N ⁺ R ⁰¹ R ¹³ R ⁷ R ⁸ or a phosphonium group: P ⁺ R ^α R ^β R ^γ R ^δ with R ^α , R ^β , R ^γ and R ^δ , identical or different, representing a hydrogen atom or a (C ₁ -C ₄ ) alkyl group; or v) a thiol protecting group; it being understood that when the compound of formula (I), (II) or (III) contains other cationic parts, it is associated with one or more anionic counter-ions making it possible to attain the electroneutrality of formula (I ), (II) or (III).

Another subject of the invention is a dye composition comprising, in a suitable cosmetic medium, at least one fluorescent dye comprising a heterocyclic group of formula (I), (II) or (III) as defined above, and optionally a reducing agent .

The invention also relates to new fluorescent dyes of formula (I), (II) or (III) as defined above. The dyeing process according to the invention makes it possible to visibly stain dark keratin materials, in particular dark human keratin fibers, especially dark hair.

In addition, the process of the invention makes it possible to obtain a coloration of the keratin materials, in particular human keratinous fibers, in particular the hair, without degrading said material, which is persistent with respect to shampoos, of the common aggressions (sun, perspiration). , and other hair treatments. The process of the invention also makes it possible to obtain a lightening of keratin materials such as keratin fibers, especially dark keratinous fibers, and more especially dark hair.

For the purposes of the invention, the term "dark keratin material" is understood to mean that which has an enumerated luminescence L ^* in the CIE system L ^* a ^* b ^* , less than or equal to 45 and preferably less than or equal to 40, while also knowing that L ^* = 0 is equivalent to black and L ^* = 100 is white.

For the purposes of the invention, the term naturally or artificially dark hair, hair whose pitch is less than or equal to 6 (dark blonde) and preferably less than or equal to 4 (chestnut).

The lightening of the hair is evaluated by the variation of "pitch" before and after application of the compound of formula (I), (II) or (III).

The notion "tone" is based on the classification of natural nuances, a tone separating each nuance from that which follows or immediately precedes it. This definition and the classification of natural shades is well known to hair professionals and published in the book "Science of hair treatments" Charles ZVIAK 1988, Ed Masson, p. 215 and 278.

Heights range from 1 (black) to 10 (very light blond), a unit corresponding to a tone; the higher the number, the clearer the nuance.

An artificially colored hair is a hair whose color has been modified by a coloring treatment, for example a coloration with direct dyes or oxidation dyes.

Preferably, the composition must, after application to hair, for example chestnut, bring to the results below.

- We are interested in the reflectance performance of hair when irradiated with visible light in the wavelength range of 400 to 700 nanometers.

The reflectance curves are then compared as a function of the wavelength, of the hair treated with the composition of the invention and of the untreated hair.

The curve corresponding to the treated hair must show a reflectance in the range of wavelengths ranging from 450 to 700 nanometers greater than the curve corresponding to untreated hair.

- This means that, in the wavelength range of 450 to 700 nanometers, there is at least one range where the reflectance curve corresponding to the treated hair is greater than the reflectance curve corresponding to untreated hair. The term "superior" means a difference of at least 0.05% reflectance, and preferably at least 0.1%. This does not prevent that it can exist in the range of wavelength from 450 to 700 nanometers, at least one range where the reflectance curve corresponding to the treated hair is superimposable, or less than the reflectance curve corresponding to the untreated hair.

Preferably, the wavelength where the difference is greatest between the reflectance curve of the treated hair and that of the untreated hair is in the wavelength range of 450 to 650 nanometers, and preferably in the wavelength range from 450 to 620 nanometers.

For the purposes of the present invention, and unless a different indication is given:

the "aryl" or "heteroaryl" radicals or the aryl or heteroaryl part of a radical may be substituted by at least one substituent carried by a carbon atom chosen from:

An alkyl radical in dC-1β, preferably in C ₁ -C ₄ , optionally substituted by one or more radicals chosen from hydroxyl, C ₁ -C ₂ alkoxy, (C ₂ -C ₄ ) poly (C ₂ -C ₄ ) -alkyl, acylamino, amino radicals; substituted by two identical or different alkyl radicals, in dC ₄ , optionally bearing at least one hydroxyl group or, the two radicals being able to form, with the nitrogen atom to which they are attached, a heterocycle comprising from 5 to 7 members preferably 5 or 6-membered, optionally substituted saturated or unsaturated optionally comprising another heteroatom identical to or different from nitrogen; A halogen atom such as chlorine, fluorine or bromine;

• a hydroxyl group; a C ₁ -C ₂ alkoxy radical;

A C ₁ -C ₂ alkylthio radical; a (C ₂ -C ₄ ) polyhydroxyalkoxy radical; An amino radical;

A 5- or 6-membered heterocycloalkyl radical; a 5- or 6-membered optionally cationic heteroaryl radical, preferentially imidazolium, and optionally substituted with a (C ₁ -C ₄ ) alkyl radical, preferably methyl; An amino radical substituted with one or two identical or different C ₁ -C ₆ alkyl radicals optionally bearing at least: i) a hydroxyl group; ii) an amino group optionally substituted with one or two C ₁ -C ₃ alkyl radicals; optionally substituted, said alkyl radicals being able to form, with the nitrogen atom to which they are attached, an optionally substituted 5 to 7-membered heterocyclic ring, saturated or unsaturated, optionally comprising at least one other heteroatom different from or different from nitrogen, an acylamino radical (-NR-COR ') in which the radical R is a hydrogen atom, a C ₁ -C ₄ alkyl radical optionally bearing at least one hydroxyl group and the radical R' is an alkyl radical; C ₁ -C ₂ ; a carbamoyl radical ((R) ₂ N-CO-) in which the radicals R, which may be identical or different, represent a hydrogen atom or a C ₁ -C ₄ alkyl radical optionally carrying at least one hydroxyl group; an alkylsulfonylamino radical

(R ¹ SO ₂ -NR-) in which the radical R represents a hydrogen atom, a C ₁ -C ₄ alkyl radical optionally bearing at least one hydroxyl group and the radical R 'represents a C ₁ -C ₄ alkyl radical; ₁ -C ₄ , a phenyl radical; an aminosulphonyl radical ((R) ₂ N-SO ₂ -) in which the R radicals, which may be identical or different, represent a hydrogen atom, a C ₁ -C ₄ alkyl radical optionally carrying at least one hydroxyl group,

A carboxylic radical in acid or salified form (preferably with an alkali metal or an ammonium, substituted or unsubstituted);

• a cyano group; A polyhaloalkyl group comprising from 1 to 6 carbon atoms and from 1 to 6 halogen atoms, which are identical or different, the polyhaloalkyl group is, for example, trifluoromethyl; the cyclic or heterocyclic part of a non-aromatic radical may be substituted by at least one substituent carried by a carbon atom chosen from the following groups: hydroxy, (C ₁ -C ₄ ) alkoxy, (poly) hydroxyalkoxy (C ₂ -C ₄₎ an alkylthio radical in dC ₂ ; Alkylcarbonylamino (RCO-NR'-) in which the radical R 'is a hydrogen atom, an alkyl radical in dC ₄ optionally bearing at least one hydroxyl group and the radical R is a C ₁ -C alkyl radical; ₂ , amino substituted with two identical or different alkyl groups in dC ₄ optionally bearing at least one hydroxyl group, said alkyl radicals being able to form, with the nitrogen atom to which they are attached, a heterocycle comprising from 5 to 7 members, optionally substituted saturated or unsaturated optionally comprising at least one other heteroatom different or different from nitrogen; Alkylcarbonyloxy (RCO-O-) in which the radical R is an alkyl radical

CrC ₄ , amino substituted with two identical or different C ₁ -C ₄ alkyl groups optionally bearing at least one hydroxyl group, said alkyl radicals being able to form, with the nitrogen atom to which they are attached, a heterocycle comprising from 5 to 7 members optionally substituted, saturated or unsaturated optionally comprising at least one other heteroatom different or different from nitrogen; alkoxycarbonyl (RO-CO-) in which the radical R is a C ₁ -C ₄ alkyl radical, amino substituted with two identical or different C ₁ -C ₄ alkyl groups optionally carrying at least one hydroxyl group, said alkyl radicals being capable of forming with the nitrogen atom to which they are attached, an optionally substituted 5- to 7-membered heterocyclic ring, saturated or unsaturated optionally comprising at least one other heteroatom different or different from nitrogen;

a cyclic, heterocyclic radical or a non-aromatic part of an aryl or heteroaryl radical may also be substituted with one or more oxo or thioxo groups;

an "aryl" radical represents a mono or polycyclic group, condensed or not, comprising from 6 to 22 carbon atoms, and of which at least one ring is aromatic; preferably the aryl radical is a phenyl, biphenyl, naphthyl, indenyl, anthracenyl, or tetrahydronaphthyl;

a "diarylalkyl" radical represents a group comprising, on the same carbon atom of an alkyl group, two identical or different aryl groups, such as diphenylmethyl or 1,1-diphenylethyl;

a "heteroaryl radical" represents a mono or polycyclic group, condensed or not, optionally cationic, comprising from 5 to 22 members, from 1 to 6 heteroatoms chosen from nitrogen, oxygen, sulfur and selenium, and at least one ring of which is aromatic; preferably heteroaryl is selected from acridinyl, benzimidazolyl, benzobistriazolyl, benzopyrazolyl, benzopyridazinyle, benzoquinolyl, benzothiazolyl, benzotriazolyl, benzoxazolyl, pyridinyl, tetrazolyl, dihydrothiazolyl, imidazopyridinyl, imidazolyl, indolyl, isoquinolyl, naphthoimidazolyle, naphthooxazolyle, naphthopyrazolyle, oxadiazolyl, oxazolyl, oxazolopyridyl phenazinyl, phenoxazolyl, pyrazinyl, pyrazolyl, pyrilyl, pyrazoyltriazyl, pyridyl, pyridinoimidazolyl, pyrrolyl, quinolyl, tetrazolyl, thiadiazolyl, thiazolyl, thiazolopyridinyl, thiazoylimidazolyl, thiopyrylyl, triazolyl, xanthylyl and its ammonium salt;

a "diheteroarylalkyl" radical represents a group comprising, on the same carbon atom of an alkyl group, two heteroaryl groups, identical or different, such as difurylmethyl, 1,1-difurylethyl, dipyrrolylmethyl, dithienylmethyl;

a "cyclic radical" is a non-aromatic, mono or polycyclic cycloalkyl radical, condensed or not, containing from 5 to 22 carbon atoms, which may contain from 1 to several unsaturations; particularly the cyclic radical is cyclohexyl; a "cyclic sterically hindered" radical is a cyclic radical, aromatic or not, substituted or unsubstituted, hindered by steric effect or constraint, comprising from 6 to 14 members, which can be bridged, as sterically hindered radicals, mention may be made of bicyclo [1.1.0] butane, mesylates such as 1,3,5-trimethylphenyl, 1,3,5-triterbutylphenyl, 1,3,5-isobutylphenyl, 1,3,5-trimethylsillylphenyl and adamantyl ;

a "heterocyclic radical" is a non-aromatic mono or polycyclic radical, condensed or not, containing from 5 to 22 members, containing from 1 to 6 heteroatoms chosen from nitrogen, oxygen, sulfur and selenium ;

an "alkyl radical" is a linear or branched C ₁ -C ₁₆ hydrocarbon radical, preferably a C ₁ -C ₈ hydrocarbon radical;

the expression "optionally substituted" ascribed to the alkyl radical, meaning that said alkyl radical may be substituted with one or more radicals chosen from the radicals i) hydroxy, ii) alkoxy C ₁ -C ₄ , iii) acylamino, iv) amino optionally substituted with one or two identical or different C ₁ -C ₄ alkyl radicals, alkyl radicals which can form with the nitrogen atom which carries them a 5- to 7-membered heterocycle, optionally comprising another heteroatom

+ different or different from nitrogen; v) or a quaternary ammonium group -N R'R "R '",

M for which R ', R ", R'", identical or different, represent an atom

+ hydrogen, or a C ₁ -C ₄ alkyl group, or else -N R'R "R '" forms a heteroaryl such as imidazolium optionally substituted with a dC ₄ alkyl group, and M represents the counter-ion of the acid organic, mineral or corresponding halide;

an "alkylene chain" represents a divalent C ₁ -C ₁₈ chain; particularly in CrC ₆ , more particularly in CrC ₂ when the chain is linear; optionally substituted by one or more, identical or different, halogen atoms or groups selected from hydroxy, alkoxy, (di) (C ₁ -C ₄ ) (alkyl) amino, R ^a -Z ^a -C (Z ^b ) - with Z ^a , Z ^b , identical or different, representing an oxygen atom, sulfur, or a group NR ^a ', and R ^a , representing an alkali metal, a hydrogen atom, or an alkyl group and R ^a representing a hydrogen atom or an alkyl group;

an "alkoxy radical" is an alkyl-oxy or alkyl-O- radical for which the alkyl radical is a hydrocarbon radical, linear or branched, in C ₁ -C ₁ 6 preferentially in C ₁ -C 6; an "alkylthio radical" is an alkyl-S- radical for which the alkyl radical is a hydrocarbon radical, linear or branched, in CrCi ₆ preferentially in CrC ₈ ; when the alkylthio group is optionally substituted, this implies that the alkyl group is optionally substituted as defined above;

the boundaries delimiting the range of a range of values lie within this range of values;

an "organic or inorganic acid salt" is more particularly chosen from a salt derived from i) hydrochloric acid HCl, ii) hydrobromic acid HBr, iii) sulfuric acid H ₂ SO ₄ , iv) from alkylsulfonic acids: Alk-S (O) ₂ OH such as methylsulfonic acid and ethylsulfonic acid; v) arylsulfonic acids: Ar-S (O) ₂ OH such as benzene sulfonic acid and toluene sulfonic acid; (vi) citric acid; vii) succinic acid; viii) tartaric acid; ix) lactic acid, x) alkoxysulfinic acids: Alk-OS (O) OH such as methoxysulfinic acid and ethoxysulfinic; xi) aryloxysulfinic acids such as tolueneoxysulfinic acid and phenoxysulfinic acid; xii) phosphoric acid H ₃ PO ₄ ; xiii) acetic acid CH ₃ COOH; xiv) triflic acid CF ₃ SO ₃ H and xv) tetrafluoroboric acid HBF ₄ ;

an "anionic counterion" is an anion or an anionic group associated with the cationic charge of the dye; more particularly the anionic counterion is selected from i) halides such as chloride, bromide; ii) nitrates; iii) sulfonates, among which C ₁ -C ₆ alkylsulfonates: AIk-S (O) ₂ O ^", such as methylsulfonate or mesylate and ethyl sulfonate; iv) arylsulfonates: Ar-S (O) ₂ ^O" as benzenesulfonate and toluenesulfonate or tosylate; v) citrate; vi) succinate; (vii) tartrate; viii) lactate; ix) alkyl sulphates: Alk-OS (O) O ^- such as methysulphate and ethylsulphate; x) arylsulphates: Ar-OS (O) O ^- such as benzenesulphate and toluenesulphate; xi) alkoxysulphates: Alk - OS (O) ₂ O ^- such as methoxy sulfate and ethoxysulphate; xii) aryloxysulphates: Ar - OS (O) ₂ O ^- (xiii) phosphate; (xiv) acetate; xv) triflate; and xvi) borates such as tetrafluoroborate. Heterocyclic fluorescent dyes of formula (I), (II) or (III) are compounds capable of absorbing in UV or visible radiation at a wavelength λ _a bs of between 250 and 800 nm and capable of retransmit in the visible range at a transmission wavelength λ _em between 400 and 800 nm.

Preferably, the heterocyclic group-containing fluorescent compounds of the invention are dyes capable of absorbing in the visible range λ _a bs of between 400 and 800 nm and of reemitting in the visible λ _em between 400 and 800 nm. More preferentially, the heterocyclic fluorescent dyes of formula (I), (II) or (III) are dyes capable of absorbing at a λ _a bs of between 420 nm and 550 nm and of reemitting in the visible at λ _em between 470 and 600 nm. A particular embodiment of the invention relates to heterocyclic fluorescent dyes of formula (I), (II) or (III) in which m is 0.

According to a particular embodiment of the invention, the fluorescent dyes of the invention, the heterocycle of formula:

represents a group or not,

optionally substituted; in particular the heterocycle is monocyclic, saturated, and comprises in total two nitrogen atoms and is formed from 5 to 8 members. In particular, the heterocyclic is chosen from piperazinyl, homopiperazinyl, hexahydro-1,4-diazepinyl, and piperazinium, homopiperazinium or hexahydro-1,4-diazepinium optionally substituted with a (dC ₄ ) alkyl group. According to another embodiment, thiols fluorescent dyes having a heterocyclic group of formula (I), (II) or (III), the heterocycle of which:

heterocyclic; monocyclic,

saturated, comprising in total a single nitrogen atom of 5 to 7 members.

In particular, the heterocyclic is chosen from pyrrolidinyl, piperidyl and azepanyl.

The fluorescent compounds of the invention of formula (III) contain a SY function which may be in the covalent -SY or ionic -S ^" Y ^{+ form} depending on the nature of Y and the pH of the medium.

One particular embodiment relates to thiols fluorescent dyes having a heterocyclic group of formula (III) with SY function where Y represents a hydrogen atom, or an alkali metal. Advantageously, Y represents a hydrogen atom.

According to another particular embodiment of the invention, in formula (III) above, Y is a protective group known to those skilled in the art, for example those described in the "Protective Groups in Organic Synthesis", TW Greene, John Willey & Sons ed., NY, 1981, pp.193-217;

"Protecting Groups", P. Kocienski, Thieme, ^3rd ed., 2005, c. 5.

Especially when Y represents a protective group of the thiol function, Y is chosen from the following radicals:

• (CrC ₄ ) alkylcarbonyl; • (CrC ₄ ) alkylthiocarbonyl;

(C 1 -C ₄ ) alkoxycarbonyl;

• (CrC ₄ ) alkoxythiocarbonyl;

(C 1 -C ₄ ) alkylthiothiocarbonyl;

• (di) (C ₁ -C ₄ ) (alkyl) aminocarbonyl; (Di) (CrC ₄ ) (alkyl) aminothiocarbonyl;

Arylcarbonyl as phenylcarbonyl;

Aryloxycarbonyl;

Aryl (C ₁ -C ₄ ) alkoxycarbonyl;

(Di) (CrC ₄ ) (alkyl) aminocarbonyl as dimethylaminocarbonyl; • (Ci-C ₄₎ (alkyl) arylaminocarbonyl;

• carboxy;

• SO ₃ ; M ⁺ with M ⁺ representing an alkali metal such as sodium or potassium, or else M 'of formula (III) and M ⁺ are absent; Optionally substituted aryl such as phenyl, dibenzosuberyl, or

1,3,5-cycloheptatrienyl,

Optionally substituted heteroaryl; including in particular cationic or non-cationic heteroaryl, comprising from 1 to 4 following heteroatoms: i) monocyclic with 5, 6 or 7 members such as furanyl or furyl, pyrrolyl or pyrryl, thiophenyl or thienyl, pyrazolyl, oxazolyl, oxazolium, isoxazolyl, isoxazolium thiazolyl, thiazolium, isothiazolyl, isothiazolium, 1,2,4-triazolyl, 1,2,4-triazolium, 1,2,3-triazolyl, 1,2,3-triazolium, 1,2,4-oxazolyl, 1 , 2,4-oxazolium, 1,2,4-thiadiazolyl, 1,2,4-thiadiazolium, pyrylium, thiopyridyl, pyridinium, pyrimidinyl, pyrimidinium, pyrazinyl, pyrazinium, pyridazinyl, pyridazinium, triazinyl, triazinium, tetrazinyl, tetrazinium, azepine azepinium, oxazepinyl, oxazepinium, thiepinyl, thiepinium, imidazolyl, imidazolium; ii) 8 to 1-membered bicyclic compounds such as indolyl, indolinium, benzoimidazolyl, benzoimidazolium, benzoxazolyl, benzoxazolium, dihydrobenzoxazolinyl, benzothiazolyl, benzothiazolium, pyridoimidazolyl, pyridoimidazolium, thienocycloheptadienyl, these mono or bicyclic groups being optionally substituted by one or more groups such as (CrC ₄ ) alkyl as methyl, or polyhalogeno (CrC ₄ ) alkyl as trifluoromethyl; iii) or tricyclic ABC following:

wherein the two rings A, C 'optionally comprise a heteroatom, and the ring B is a 5-, 6- or 7-membered particularly 6-membered ring and contains at least one heteroatom such as pyperidyl, pyranyl; Optionally substituted heterocycloalkyl, optionally cationic, the heterocycloalkyl group represents in particular a saturated or partially saturated 5-, 6- or 7-membered monocyclic group comprising from 1 to 4 heteroatoms chosen from oxygen, sulfur and nitrogen, such as di / tetrahydrofuranyl, di / tetrahydrothiophenyl, di / tetrahydropyrrolyl, di / tetrahydropyranyl, di / tetra / hexahydrothiopyranyl, dihydropyridyl, piperazinyl, piperidinyl, tetramethylpiperidinyl, morpholinyl, di / tetra / hexahydroazepinyl, di / tetrahydro-pyrimidinyl, these groups being optionally substituted by one or more groups such as (C ₁ -C ₄ ) alkyl, oxo or thioxo; or the heterocycle represents the following group:

wherein R ^'c, R' ^d, R ^e, R ^f, R ^'9 and R' ^h, identical or different, represent a hydrogen atom or a (C ₁ -C ₄₎ alkyl, or else two group R ' ⁹ with R' ^h , and / or R ' ^e with R' ^f form an oxo or thioxo group, or else R ' ⁹ with R' ^e together form a cycloalkyl; and v represents an integer inclusive of between 1 and 3; preferentially R ' ^c to R' ^h represent a hydrogen atom; and An represents a counterion;

isothiouronium -C (NR ' ^c R' ^d ) = N ⁺ R ' ^e R'^f; An ^"with R ^'c, R' ^d, R ^'e and R' ^f, like or different, represent a hydrogen atom or a (Ci-C ₄₎ alkyl; preferably, R ^'c to R' ^f represent a hydrogen atom, hydrogen, and An ^" represents a counterion;

isothiourea -C (NR ' ^c R' ^d ) = NR ' ^e with R' ^c , R ' ^d and R' ^e as defined previously;

Optionally substituted (di) aryl (CrC ₄ ) alkyl such as 9-anthracenylmethyl, phenylmethyl or diphenylmethyl, optionally substituted with one or more groups chosen in particular from (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) BlCOXy, such as methoxy, hydroxy, (C ₁ -C ₄ ) alkylcarbonyl, and (di) (C ₁ -C ₄ ) (alkyl) amino such as dimethylamino;

Optionally substituted (di) heteroaryl (CrC ₄ ) alkyl, the heteroaryl group is in particular, cationic or non-cationic, monocyclic, comprising 5 or 6-membered and 1 to 4 heteroatoms selected from nitrogen, oxygen and sulfur, such as pyrrolyl, furanyl, thiophenyl, pyridyl, pyridyl N-oxide such as 4-pyridyl or 2-pyridyl-N- oxide, pyrylium, pyridinium, triazinyl, optionally substituted with one or more groups such as alkyl particularly methyl, advantageously (di) heteroaryl (CrC ₄ ) alkyl is (di) heteroaryl-methyl or (di) heteroarylethyl;

CR ¹ R ² R ³ with R ¹ , R ² and R ^{3, which may be} identical or different, representing a halogen atom or a group chosen from:

- (C ₁ -C ₄ ) alkyl; - (C ₁ -C ₄ ) alkoxy;

optionally substituted aryl such as phenyl optionally substituted by one or more groups such as (CrC ₄ ) alkyl, (C ₁ -C ₄ ) alkoxy, hydroxy;

optionally substituted heteroaryl such as thiophenyl, furanyl, pyrrolyl, pyranyl or pyridyl, optionally substituted with a group

(Ci-C ₄₎ alkyl;

- P (Z ¹ ) R ' ¹ R' ² R ' ³ with R' ¹ , and R ' ^{2 the} same or different represent a hydroxyl group, (CrC ₄ ) alkoxy or alkyl, R' ³ represents a hydroxyl group or (CrC ₄ ) alkoxy, and Z ¹ represents an oxygen or sulfur atom;

Sterically hindered cyclic such as the adamantyl group; and

Optionally substituted alkoxy (CrC ₄ ) alkyl such as methoxymethyl (MOM), ethoxyethyl (EOM) and isobutoxymethyl.

According to a particular embodiment, the heterocyclic protected thiol protected fluorescent dyes of formula (III) contain a cationic aromatic 5- or 6-membered monocyclic moiety Y i) heteroaryl comprising from 1 to 4 heteroatoms chosen from oxygen, sulfur and nitrogen, such as oxazolium, isoxazolium, thiazolium, isothiazolium, 1,2,4-triazolium, 1,2,3-triazolium, 1,2,4-oxazolium, 1,2,4-thiadiazolium, pyrylium, pyridinium pyrimidinium, pyrazinyl, pyrazinium, pyridazinium, triazinium, tetrazinium, oxazepinium, thiepinyl, thiepinium, imidazolium; ii) cationic 8 to 1 membered bicyclic heteroaryl such as indolinium, benzoimidazolium, benzoxazolium, benzothiazolium, these mono or bicyclic heteroaryl groups being optionally substituted with one or more groups such as alkyl as methyl, or polyhalo (C ₁ -C ₄ ) alkyl as trifluoromethyl; iii) or heterocyclic according to:

wherein R ' ^c and R' ^d , identical or different, represent a hydrogen atom or a group (dC ₄ ) alkyl; preferentially R ' ^c to R' ^d represent a (dC ₄ ) alkyl group such as methyl; and An represents a counterion.

Especially Y represents a group selected from oxazolium, isoxazolium, thiazolium, isothiazolium, 1,2,4-triazolium, 1,2,3-triazolium, 1,2,4-oxazolium, 1,2,4-thiadiazolium, pyrylium, pyridinium , pyrimidinium, pyrazinium, pyridazinium, triazinium and imidazolium, benzoimidazolium, benzoxazolium, benzothiazolium, these groups being optionally substituted by one or more (CrC ₄ ) alkyl groups including methyl.

In particular, the fluorescent dyes of formula (III) contain a group Y representing an alkali metal or a protective group such as:

> (Ci-C ₄₎ alkylcarbonyl such as methylcarbonyl or ethylcarbonyl; arylcarbonyl, such as phenylcarbonyl;

> (Ci-C ₄₎ alkoxycarbonyl;

> aryloxycarbonyl;

alkoxycarbonyl;

> (di) (C ₁ -C ₄ ) (alkyl) aminocarbonyl as dimethylaminocarbonyl; (C ₁ -C ₄ ) (alkyl) arylaminocarbonyl;

optionally substituted aryl such as phenyl;

monocyclic 5- or 6-membered heteroaryl such as imidazolyl or pyridyl;

Cationic monocyclic 5- to 6-membered heteroaryl such as pyrylium, pyridinium, pyrimidinium, pyrazinium, pyridazinium, triazinium, imidazolium; these groups being optionally substituted with one or more, identical or different, (CrC ₄ ) alkyl groups such as methyl;

8 to 1-membered cationic bicyclic heteroaryl such as benzoimidazolium, or benzoxazolium; these groups being optionally substituted with one or more identical or different groups (CrC ₄ ) alkyl such that methyl;

cationic heterocycle of following formula:

> isothiouronium -C (NH ₂ ) = N ⁺ H ₂ ; An ^" isothiourea -C (NH ₂ ) = NH;

> SO ₃ ^" , M ⁺ with M ⁺ representing an alkali metal such as sodium or potassium, or else M 'of formula (III) and M ⁺ are absent.

According to one particular embodiment of the invention, the dyes of the invention belong to the formula (I), (II) or (III), contain the ethylene group connecting the pyridinium portion to the phenyl in the ortho or para position or in the 4-position. -4 ', 2-2', 4-2 'or 2-4'.

Another particular embodiment of the invention relates to disulfide dyes of formula (I) symmetrical ie R _a, R _9, R _'g, R h, R'H, R, R', Ri, R2, R3, R ₄ , T ₃ , m, n are identical to R ' _a , R " _g , R'" _g , R " _h , R '" _h , R ",, R'", R'1, R'2, R's, R ' ₄ , T _b , m' and n 'respectively. By way of example of fluorescent dyes of the invention, mention may in particular be made of the following compounds:

An ^"

48

49

With M 'and An-, identical or different, representing an anionic counterion; and M ⁺ representing an alkali metal.

The protected thiol dyes of formula (IM ") can be synthesized in two steps: the first step of preparing the unprotected thiol dye (IH ') according to the methods known to those skilled in the art, for example" Thiols and organic Sulfides "," Thiocyanates and Isothiocyanates, organic ", Ullmann's Encyclopedia, Wiley-VCH, Weinheim, 2005. And the second step of protecting the thiol function according to conventional methods known to those skilled in the art to lead to protected thiol dyes of formula (IM "). By way of example, to protect the thiol -SH function of the thiol dye, the methods of the "Protective Groups in Organic Synthesis", TW Greene, John Willey & Sons ed., NY, 1981, pp.193-217; "Protecting Groups", P. Kocienski, Thieme, ^3rd ed., 2005, c. 5.

We can illustrate this method by the method consisting of i) generating heterocyclic thiols fluorescent dyes of formula (IH ') by reduction of a heterophylic, heterocyclic fluorescent dye bearing a disulfide function -SS- such that (I ¹ ) and ii) protecting, according to conventional methods, said thiol function of (IM ') to obtain protected thiol fluorescent dyes of formula (MI "):

with R 1, R ₂ , R ₃ , R ₄ , R ₃ , R ₉ , R ' _g , Rh, R 1, R 1, R', m, n, Het and M 'are as defined above; Y 'represents a protecting group of thiol function; and R represents a leaving group nucleofuge, such as, for example, mesylate, tosylate, triflate or halide.

According to another possibility, a protected thiol compound (b) can be reacted with a protective group Y 'as defined previously prepared according to one of the procedures described in the works cited above, said protected thiol compound comprising at least one nucleophilic function with a a sufficient amount, preferably equimolar, of a "reactive fluorescent chromophore" or a compound comprising such a "reactive fluorescent chromophore." In other words (a) comprises an electrophilic function to form a covalent bond Σ can be schematized below:

with R, R _2, R _3, R _4, R _3, R _9, R _'g, R h, R'H R, R' ,, m, n, Het, Y 'and M' are as previously defined ; 5Vw representing a nucleophilic group; £ representing an electrophilic group; and Σ the bond generated after nucleophilic attack on the electrophile.

By way of example, the covalent bonds that can be generated are listed in the table below from the condensation of electrophiles with nucleophiles:

Carboxylic Acids Amarboxamides

Carboxylic Acids Alcohols Esters

Carbodiimides M-acylurea or anhydride carboxylic acids

Diazoalkanes Carboxylic Acids Esters

Epoxides Thiols fhioethers

Haloacetamides Thiols fhioethers

Imidic Esters Amine Amines

Urea Amino Isocyanates

Isocyanates Alcohols Urethanes

Isothiocyanates Amines fhiourées

Maleimides Thiols fhioethers

Sulfonic Esters Amines Alkylamines

Sulphonic esters Thiols fhioethers

Sulphonic Esters Ester Carboxylic Acids

Sulphonic Esters Alcohols Ethers

Sulfonamide halides Amines Sulfonamides activated esters of general formula -CO-Part with Part representing a leaving group such as oxysuccinimidyl, oxybenzotriazolyl, optionally substituted aryloxy;

^** Acyl azides can rearrange to give isocyanates.

An alternative to this method is to use a fluorescent chromophore having an electrophilic acrylate function (-OCO-C = C-) on which an addition reaction is performed which will generate a Σ bond.

It is also possible to use a thiol reagent Y'-SH comprising a group Y 'as defined above, the nucleophilic function SH of which can react on the carbon atom in alpha of the halogen atom carried by the fluorescent chromophore (at ¹ ) to yield the protected thiol fluorescent dye of formula (IM "):

with R ₁ , R ₂ , R ₃ , R ₄ , R ₃ , R ₉ , R ' _g , Rh, R', T ₃ , R ₁ , R ' ₁ , m, n, Het, Y', (M ₁ ") and M 'are as defined above, and HaI represents a nucleofugal halogen atom such as bromine, iodine or chlorine.

More particularly, it will be possible to substitute a nucleofugal leaving group with a thiourea group (S = C (NRR) NRR) to generate the isothiouroniums. For example, if the thiourea group is a thioimidazolium (β), the reaction scheme is as follows:

with R _a , R ' _c , R'd, Rg, R'g, Rh, R'h, Ri, R'i, m, n, Het, HaI, An ^" and M' are as defined above.

An alternative is to use in place of the halide comprising the fluorescent chromophore (a ¹ ) a chromophore comprising another type of nucleofuge such as tosylate, mesylate. In accordance with another possibility, certain protected heterocyclic thiol thiols (IM '-) dyes can be obtained by reacting a protected thiol compound with a compound carrying two carboxylic acid functions activated by conventional methods (for example reaction with a carbodiimide or with thionyl chloride) The resulting product (d) is then reacted with a heterocyclic fluorescent chromophore carrying a nucleophilic function (ç), for example of the primary or secondary amine type, or of the aliphatic alcohol type or aromatic like phenol. J _n -SY ¹ (III ¹¹¹ )

with R ₁ , R ₂ , R ₃ , R ₄ , R ₃ , R ₉ , R ' _g , Rh, R', R ', R', Het, T ₃ , Y ', m, n, M' , ^< £, 5VM and (Ml '") as defined above.

According to another possibility, the protected heterocyclic thiols fluorescent dyes of formula (III) can be obtained by reaction of a compound comprising a thiol group protected by a Y 'group, and a previously activated hydroxy group in nucleofugal leaving group (cT). , such as, for example, mesylate, tosylate, triflate or halide with a fluorescent chromophore bearing a nucleophilic amino function on the heterocyclic part of Het.

With R 1, R ₂ , R ₃ , R ₄ , R ₃ , R ₉ , R'g, Rh, R ', R', R ', Het, T ₃ , Y', n, M ', Σ and E are as previously defined.

By way of example, a compound containing a protected thiol group contains a leaving group R, such as, for example, mesylate, tosylate, or triflate, which can undergo the nucleophilic attack of the amine carried by the styryl fluorescent chromophore:

Another alternative comes from the use of halides as nucleofugal leaving group on a thiol compound which can be substituted by a primary amine function, for example carried by a styryl fluorescent chromophore:

According to another possibility, the protected thiol fluorescent dyes of formula (III) according to the invention may be obtained by reaction of a compound comprising a thiol group Y as defined above and an electrophilic group (Q with a compound comprising a group By way of example, an aldehyde or ketone may be condensed when G represents an oxygen atom with an "activated methylene" such as alkylpyridinium (e) to generate an ethylene bond> C = C <. Known as "Knoevenagel" condensation, the term "activated methylenes" is understood to mean, for example, those mentioned in patent DE19951 134, especially 1,2-dialkylpyridinium and in particular 1,2-dimethylpyridinium:

with R ₁ , R ₂ , R ₃ , R ₄ , R ₃ , R ₉ , R ' _g , Rh, R', R ,, R ',, Het, T ₃ , m, n, Y and M' such than defined above and G representing an oxygen atom, sulfur or a group N (R) with R representing a hydrogen atom or a group (C ₁ - C ₄ ) alkyl.

An alternative to this method is to carry out i) a "Knoevenagel" condensation of an aldehyde or a ketone comprising a Het heterocycle containing a nucleophilic amino group {g} with an "activated methylene" such as alkylpyridinium (e) to lead to the styryl-heterocyclic intermediate (h). The latter can then ii) react on a cyclic monomer containing at least one thiolactam function, to conduct after ring opening to the heterocyclic thiol fluorescent dye (MIa):

With R _1, R _2, R _3, R _4, R ₃ R _9, R _'g, R _h, R'H, R ,, R' ,, Het, n and M 'as previously defined, G and G , the same or different, an oxygen atom, sulfur or a group N (R) with R representing a hydrogen atom or a group (C ₁ - C ₄ ) alkyl.

Alternatively, when the reagent (g ¹ ) comprises an Het group with an exocyclic amino group, the amide, thioamide, guanidine or amidine group fluorescent dye is obtained

With R 1, R ₂ , R ₃ , R ₄ , R ₃ , R ₉ , R ' _g , Rh, R', R ', R', Het, n, M ', G and G', as defined previously and R 'represents a hydrogen atom, or an alkyl group. It being understood that the amine of the heterocycle of the reagent (ç) can be protected and then deprotected.

Reference may be made to the book Advanced Organic Chemistry, J. March, 4 ^th Ed, John Wiley & Sons, 1992, or TW Greene "Protective Groups in Organic Synthesis" for more details on the operating conditions implemented to the processes mentioned above. The thiol fluorescent dyes formed can be converted to protected thiol stain -SY 'by protecting the thiol -SH using conventional protecting groups.

The protected thiol dyes can be deprotected by conventional routes.

The disulfide dyes of formula (I) can be synthesized in two stages. The first step of preparing the unprotected thiol dye (III) according to the methods described above. And the second step of oxidizing the unprotected thiol dye (III) to form the symmetrical disulfide dye of formula (I ¹ ). The oxidation of a thiol to disulfide is done according to conventional methods known to those skilled in the art, for example using hydrogen peroxide.

According to another possibility, an equivalent of a disulfide compound (b ") can be reacted according to one of the procedures described in the works cited above, said disulfide compound comprising two nucleophilic functions with a sufficient amount of a" reactive fluorescent chromophore " or a compound comprising such a "reactive fluorescent chromophore" (a), such as at least two equivalents, In other words (a) comprises an electrophilic function to form a covalent bond Σ, to yield the disulfide dye. formula (I ") as can be schematized below:

with R, R _2, R 3, R _4, R _a, Rg, R _'g, R h, R'H, R, R', m, n, Het and M 'are as defined above; Nude representing a nucleophilic group; ¹ E representing an electrophilic group; and Σ the bond generated after nucleophilic attack on the electrophile. By way of example, the covalent bonds Σ that can be generated are listed in the table above from condensation of electrophiles with nucleophiles.

According to another possibility, certain fluorescent disulfide dyes (I ") can be obtained by reacting at least two equivalents of a" reactive fluorescent chromophore (ç) comprising a nucleophilic moiety with one equivalent of a dielectrophilic disulfide compound (d "). ), to give the disulfide dye (I "):

with R _1, R _2, R _3, R _4, R _3, R _9, R _'g, R _n, R' n, R, R ',, Het, m, n, M', ^<£, and 9ûι (I ") as defined above.

According to another possibility, the heterocyclic disulfide fluorescent dyes of formula (I ¹ ") can be obtained by reaction of a compound (d") comprising a disulfide group, and a previously activated hydroxy group in nucleofug leaving group Cp, as per for example with mesylate, tosylate, triflate or halide with a fluorescent chromophore (£) bearing a nucleophilic amino function on the heterocyclic part of Het.

With R _1, R _2, R _3, R _4, R _3, R _9, R _'g, R h, R'H, R ,, R' ,, Het, n, M ', and Cp are as defined previously.

By way of example, a compound containing a disulfide group contains a leaving group R, such as, for example, mesylate, tosylate or triflate, which can undergo the nucleophilic attack of the amine carried by the styryl fluorescent chromophore to yield the disulfide dye. particular (1 "a):

Another alternative comes from the use of halides as nucleofugal leaving group on a disulfide compound which may be substituted by a secondary amine function, for example carried by a styryl fluorescent chromophore:

IEL

According to another possibility, the fluorescent disulfide dyes (I) according to the invention may be obtained by reaction of a compound comprising a disulfide group as defined above and an electrophilic group (f ") with a compound comprising a nucleophilic group. By way of example, an aldehyde or ketone may be condensed when G represents an oxygen atom with an "activated methylene" such as alkylpyridinium (e) to generate an ethylene bond> C = C <. This reaction is commonly Known as "Knoevenagel" condensation "Activated methylenes" are understood to mean, for example, those mentioned in patent DE19951 134, especially 1,2-dialkylpyridinium and especially 1,2-dimethylpyridinium:

(I ¹ ) with R 1, R ₂ , R ₃ , R ₄ , R ₃ , R ₉ , R ' _g , Rh, R', R, R ', R', Het, T ₃ , m, n, (I ') and M' such that defined above and G representing an oxygen atom, sulfur or a group N (R) with R representing a hydrogen atom or a group (d-C ₄ ) alkyl.

Reference may be made to the book Advanced Organic Chemistry, J. March, 4 ^th Ed, John Wiley & Sons, 1992, or TW Greene "Protective Groups in Organic Synthesis" for more details on the operating conditions implemented to the processes mentioned above.

The disymmetrical disulfide dyes of formula (I) may be synthesized in one step by reacting an unprotected thiol fluorescent dye with a Y'-protected thiol fluorescent dye to form the disulfide dye of formula (I).

with R ₃ , R ' _a , R ₉ , R' _g , R " _g , R '" _g , Rh, R'h, R "h, R'" h, R 1, R'i, R "ι, R ι, m, m ', n, n', T ₃ , T _b , Het Het ', (I) and M' are as previously defined; Y 'represents a protecting group of thiol function.

The asymmetric disulfide dyes of formula (II) can be synthesized in one step by reacting a protected thiol fluorescent dye with an unprotected thiol compound to form the disulfide dye of formula (b).

with R ₃ , R ' _a , R ₉ , R' _g , R " _g , R '" _g , Rh, R'h, R "h, R'" h, R 1, R'i, R "ι, R "ι, R'c, m, m ', n, n', T _3, T _b, Het, Hef, (II) and m 'are as defined above; Y 'represents a protecting group of thiol function. The composition of the invention contains at least one heterocyclic fluorescent dye of formula (I), (II) or (III). In addition to the presence of at least one fluorescent dye of formula (I), (II) or (III), the composition of the invention may also contain a reducing agent. This reducing agent may be chosen from thiols, for example cysteine, homocysteine, thiolactic acid, the salts of these thiols, phosphines, bisulfite, sulphites, thioglycolic acid and its esters, especially the glycerol monothioglycolate, and thioglycerol. This reducing agent may also be chosen from borohydrides and their derivatives, such as, for example, borohydride, cyanoborohydride, triacetoxyborohydride or trimethoxyborohydride salts: sodium, lithium, potassium, calcium, quaternary ammonium salts (tetramethylammonium, tetraethylammonium, tetra butylammonium, benzyltriethylammonium); catechol borane.

The dye composition useful in the invention generally contains a quantity of heterocyclic fluorescent dye of formula (I), (II) or (III) of between 0.001 and 50% relative to the total weight of the composition. Preferably, this amount is between 0.005 and 20% by weight and even more preferably between 0.01 and 5% by weight relative to the total weight of the composition.

The dye composition may further contain additional direct dyes. These direct dyes are for example chosen from direct dyes neutral, acidic or cationic nitro-benzene dyes, neutral, acid or cationic azo direct dyes, tetraazapentamethine dyes, neutral or acidic or cationic quinone dyes, in particular neutral anthraquinone dyes, azine direct dyes, triarylmethane direct dyes, indoamine direct dyes and natural direct dyes.

Among the natural direct dyes that may be mentioned are lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogalline, protocatechaldehyde, indigo, isatin, curcumin, spinulosin, apigenidine. It is also possible to use the extracts or decoctions containing these natural dyes, and in particular poultices or extracts made from henna.

The dye composition may contain one or more oxidation bases and / or one or more couplers conventionally used for dyeing keratinous fibers.

Among the oxidation bases that may be mentioned are para-phenylenediamines, bisphenylalkylenediamines, para-aminophenols, bis-para-aminophenols, ortho-aminophenols, heterocyclic bases and their addition salts.

Among these couplers, there may be mentioned meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers, heterocyclic couplers and their addition salts. The coupler or couplers are each generally present in an amount of between 0.001 and 10% by weight of the total weight of the dye composition, preferably between 0.005 and 6%.

The oxidation base (s) present in the dyeing composition are in general each present in an amount of between 0.001% and 10% by weight relative to the total weight of the dyeing composition, preferably between 0.005% and 6% by weight.

In general, the addition salts of the oxidation bases and couplers that can be used in the context of the invention are chosen especially from the addition salts with an acid such as hydrochlorides, hydrobromides, sulphates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates and addition salts with a base such as alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, ammonia, amines or alkanolamines.

The medium suitable for dyeing, also called dyeing medium, is a cosmetic medium generally consisting of water or a mixture of water and at least one organic solvent. Examples of organic solvents that may be mentioned are lower C ₁ -C ₄ alkanols, such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, and mixtures thereof.

The solvents when present are preferably present in proportions preferably of between 1 and 40% by weight approximately relative to the total weight of the dye composition, and even more preferably between 5 and 30% by weight approximately.

According to one variant, the invention contains a reducing agent capable of reducing the disulfide bonds of keratin. This reducing agent is as defined above.

The dye composition may also contain various adjuvants conventionally used in compositions for dyeing hair, such as anionic, cationic, nonionic, amphoteric, zwitterionic surfactants or mixtures thereof, anionic, cationic, nonionic, amphoteric and zwitterionic polymers. or mixtures thereof, inorganic or organic thickeners, and in particular anionic, cationic, nonionic and amphoteric polymeric associative thickeners, antioxidants, penetrating agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as, for example, volatile or non-volatile silicones, modified or otherwise, such as aminosilicones, film-forming agents, ceramides, preserving agents, opacifying agents, conductive polymers.

The adjuvants above are generally present in an amount for each of them between 0.01 and 20% by weight relative to the weight of the composition.

Of course, one skilled in the art will take care to choose this or these optional additional compounds in such a way that the advantageous properties intrinsically attached to the dyeing composition according to the invention are not, or not substantially, impaired by the or the additions envisaged. The pH of the dyeing composition is generally between 3 and 14 approximately, and preferably between 5 and 1 1 approximately. It can be adjusted to the desired value by means of acidifying or alkalizing agents usually used for dyeing keratin fibers or else using conventional buffer systems.

Among the acidifying agents, mention may be made, by way of example, of mineral acids or organic such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, sulfonic acids.

Among the alkalinizing agents that may be mentioned, by way of example, are ammonia, alkaline carbonates, alkanolamines such as mono-, di- and triethanolamines and their derivatives, sodium or potassium hydroxides and following formula (γ):

^R ^ 1 _/ ^R a2

N - W ₃ -N

^R a4 ^R a3 ^ wherein W _a is a propylene residue optionally substituted with a hydroxy group or a C ₁ -C ₄ alkyl radical; R _a i, R _a2 . R a3 and R _a4, identical or different, represent a hydrogen atom, an alkyl radical in C ₁ -C ₄ hydroxyalkyl or C ₁ -C _4.

The dye composition may be in various forms, such as in the form of liquid, cream, gel, or in any other form suitable for dyeing keratinous fibers, and in particular hair.

According to a particular embodiment in the process of the invention, a reducing agent may be applied pre-treatment before application of the composition containing at least one heterocyclic fluorescent dye of formula (I), (II) or (III) .

This reducing agent may be chosen from thiols, for example cysteine, homocysteine, thiolactic acid, the salts of these thiols, phosphines, bisulfite, sulphites, thioglycolic acid and its esters, especially the glycerol monothioglycolate, and thioglycerol. This reducing agent may also be chosen from borohydrides and their derivatives, such as, for example, borohydride, cyanoborohydride, triacetoxyborohydride or trimethoxyborohydride salts: sodium, lithium, potassium, calcium, quaternary ammonium salts (tetramethylammonium, tetraethylammonium, tetra butylammonium, benzyltriethylammonium); catecholborane.

This pretreatment may be of short duration, in particular from 0.1 second to 30 minutes, preferably from 1 minute to 15 minutes with a reducing agent as mentioned above.

When the heterocyclic thiol fluorescent dye (III) comprises a grouping As a protector of the thiol function, the process of the invention may be preceded by a deprotection step aimed at rendering the SH function in situ.

By way of example, it is possible to deprotect the S-Y function with Y protecting group by adjusting the pH as follows:

The deprotection step can also be carried out in the course of a hair pretreatment step such as, for example, the reducing pretreatment of the hair.

According to one variant, the reducing agent is added to the dye composition containing at least one heterocyclic fluorescent dye (I), (II) or (III) at the time of use.

According to another method, the composition comprising at least one heterocyclic fluorescent dye of formula (I), (II) or (III) also contains at least one reducing agent as defined above. This composition is then applied to the hair. According to another variant, the reducing agent is applied in post-treatment, after the application of the composition containing at least one fluorescent dye of formula (I), (II) or (III). The duration of the post-treatment with the reducing agent may be short, for example from 0.1 second to 30 minutes, preferably from 1 minute to 15 minutes, with a reducing agent as described above. According to an embodiment in particular, the reducing agent is a thiol or borohydride type agent as described above.

In the dyeing process another variant is to apply the fluorescent dye of formula (I) or (II) at the same time as the reducing agent. A particular embodiment of the invention relates to a process in which the fluorescent dye of formula (I), (II) or (III) can be applied directly to hair without reducing agents, free of pre or post-treatment reducers.

A treatment with an oxidizing agent may optionally be associated. Any type of conventional oxidizing agent may be used in the art. Thus, it may be chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulphates, as well as the enzymes among which may be mentioned peroxidases, oxides, 2-electron reductases such as uricases and 4-electron oxygenases such as laccases.

The use of hydrogen peroxide is particularly preferred. This oxidizing agent may be applied to the fibers before or after the application of the composition containing at least one fluorescent dye of formula (I), (II) or (III). The application of the dye composition according to the invention is generally carried out at room temperature. It can however be carried out at temperatures ranging from 20 to 180 ° C. The invention also relates to a multi-compartment device or "kit" of dyeing in which a first compartment contains a dye composition comprising at least one heterocyclic fluorescent dye of formula (I), (II) or (III) and a second compartment contains a reducing agent capable of reducing the disulfide functions of keratin materials. One of these compartments may further contain one or more other dyes of direct dye type or oxidation dye.

It also relates to a multi-compartment device in which a first compartment contains a dye composition comprising at least one heterocyclic thiol fluorescent dye of formula (I), (II) or (III); a second compartment contains a reducing agent capable of reducing the disulfide bond of the keratin materials and / or the disulfide bond of the dyes of formula (I) or (II); a third compartment contains an oxidizing agent.

Alternatively, the dyeing device contains a first compartment containing a dye composition which comprises at least one fluorescent dye protected thiol of formula (III) and a second compartment containing an agent capable of deprotecting the protected thiol to release the thiol.

Each of the devices mentioned above can be equipped with a means for delivering the desired mixture onto the hair, for example such as the devices described in patent FR 2 586 913.

The examples which follow serve to illustrate the invention without, however, being limiting in nature. The fluorescent dyes of the examples below have been fully characterized by conventional spectroscopic and spectrometric methods.

EXAMPLES

EXAMPLES OF SYNTHESIS

Example 1 Synthesis of 4,4 '- {disulfanediylbis [ethane-2,1-diylpiperazine-4,1-diyl-4,1-phenylene (E) ethene-2,1-diyl]} bis dimethylsulfate 1-methylpyridinium)

[1]

[1]

Diagram of synthesis

- N N-

O

[1] Step 1: Synthesis of 4,4 '- [disulfanediylbis (ethane-2,1-diylpiperazine-4,1-diyl)] - dibenzaldehyde

2.5 g of 4-piperazin-1-yl-benzaldehyde, 1.37 g of 1-bromo-2 - [(2-bromoethyl) disulfanyl] ethane, 7.3 g of potassium carbonate (K ₂ CO ₃ ), and 20 ml of N-methylpyrrolidinone (NMP) are mixed at 75 ° C for 55 h. The product is purified by chromatography on silica gel (eluent: acetone / heptane 80/20 then dichlormethane / methanol 90/10). 469 mg of yellow oil are collected. The analyzes indicate that the product is compliant. Step 2: Synthesis of 4,4 '- {disulfanediylbis [ethane-2,1-diylpiperazine-4,1-diyl-4,1-phenylene (E) ethene-2,1-diyl]} bis dimethylsulfate ( 1-methylpyridinium) [1] 469 mg of 4,4 '- [disulfanediylbis (ethane-2,1-diylpiperazine-4,1-diyl)] dibenzaldehyde, 5 mL of isopropanol (iPrOH), 415 mg of methylsulfate of 1 , 4-dimethylpyridinium, 80 mg of pyrrolidine, 56 mg of acetic acid and 5 mL of dichloromethane are mixed at room temperature for 24 h and then at 40 ° C for 24 h. After cooling the mixture, 20 ml of acetone are added, the precipitate obtained is filtered, washed with 10 ml of isopropanol, then with 3 times 25 ml of acetone, and dried. 610 mg of red powder are collected. The analyzes indicate that the product is compliant.

¹ H NMR (400 MHz, MeOH ^ ₄₎ 2.68 (m, 8H), 2.78 (t, 4H), 2.95 (t, 4H), 3.37 (m, 8H), 3.68 (s, 6 H ), 4.24 (s, 6H), 7 (d, 4H), 7.16 (d, 2H), 7.62 (d, 4H), 7.82 (d, 2H), 8.01 (d, 4H), 8.56 (d, 4H)

Example 2 Synthesis of 1-methyl-4 - ((E) -2- {4- [4- (2-sulfanyl-ethyl) piperazin-1-yl] phenyl} vinyl) pyridinium methylsulfate [2]

[2]

Diagram of synthesis

Operating mode

Synthesis of 1-methyl-4 - ((E) -2- {4- [4- (2-sulfanylethyl) piperazin-1-yl] phenyl} vinyl) pyridinium salt [2]

16 mg of the compound [1] are dissolved in 10 ml of water / ethanol mixture (v / v: 1/1); 60 mg (2 eq) of 3- [bis (2-carboxyethyl) phosphino] propanoic acid hydrochloride hydrate in solution in 1 ml of water and 21 mg (4 eq) of sodium bicarbonate in solution in 1 ml of water are added to the mixture. After stirring for 30 minutes at 40 ° C. under an inert atmosphere, the analyzes indicate that the mixture contains most of the expected product [2].

LC-MS analysis: LC-DAD (400-700 nm)

Column: Waters XTerra MS C18 5μm (4.6 x 50) mm

Mobile phase: A: Water + formic acid 0.1% / B: acetonitrile

Linear gradient: T (min) A% / B%: 0 min 95/5; 8min 0/100

Flow rate: 1 ml / min.

Detection: UV diode array λ = 400-700nm

Retention time t = 3.0 min. Relative purity> 90% MS (ESI +) m / z = 285 corresponds to the mass peak of the expected product monocation [2]

EXAMPLE OF COLORING

Example 1 Coloring Process - Compound [1]

Preparation of a composition A

Preparation of a composition B

Thioglycolic acid 1 M

Sodium hydroxide qsp pH 8.5

Demineralized water qs 100g

At the time of use, compositions A (9 ml) and B (1 ml) are mixed, and then the mixture obtained is applied to a lock of 1 g of dark hair (pitch 4) for 30 minutes at room temperature. (The locks are returned and re-impregnated after 15 minutes).

After rinsing with running water and drying, a lightening of the hair thus treated is observed: the lock of pitch 4 became visually clearer than untreated control locks.

Example 2: Coloring Process with Compound [2]

10 ml of fresh solution of the compound [2] of the synthetic example are applied to a lock of 1 g of hair of pitch 4 arranged at the bottom of a bowl for 30 minutes at room temperature (the locks are returned and re-impregnated after 15 minutes). The locks are then rinsed with running water and dried. After staining, the pitch lock 4 became visually brighter than untreated control locks.

Persistence with respect to successive shampoos: The wicks thus treated are divided in two, one half is subjected to 5 successive shampoos in a cycle which comprises wetting the locks with water, washing with a conventional shampoo, rinsing with water followed by drying.

Visual Observations When shampooing, there is no visible bleeding, shampoo foam and rinsing water are not colored

The observed color is preserved and the lightening effect remains visible on the hair of pitch 4 thus treated.

Results in the L ^* a ^* b ^{* system} :

The color of the locks before and after the 5 washes was evaluated in the system

L ^* a ^* b ^* using a KONICA MINOLTA ® CM 2600 Spectrophotometer, (Illuminant

D65).

In this system L ^* a ^* b ^* , L ^* represents the intensity of the color, a ^* indicates the green / red color axis and b ^* the blue / yellow color axis. The higher the L value, the lighter or less intense the color. Conversely, the lower the value of L, the darker or more intense the color. The higher the value of a ^{* the} higher the shade is red and the higher the value of b ^* the hue is yellow. The variation of the coloration between the strands of hair HT4, stained and washed is measured by (ΔE) according to the following equation:

Δ E = V (L * - L ₀ *) ² + (a * - a ₀ *) ² + (b * - b ₀ * γ

In this equation, L ^* , a ^* and b ^* represent the measured values before staining and L ₀ ^* , ao ^* and bo ^* represent the values measured after staining or after staining and shampooing. The higher the value of ΔE, the greater the difference in color between the HT4 locks and the colored locks.

The results of the table show that there is no significant difference in color variation even after 5 shampoos. Thus the coloration and the lightening effect on the hair remain virtually unchanged which shows a very good resistance to shampoos dyes of the invention.

Reflectance results:

The lightening of the compositions according to the invention and their persistence with regard to successive shampoos were also expressed as a function of the reflectance of the hair. These reflectances are compared to the reflectance of a lock of untreated HT4 pitch hair.

Reflectance is measured using a KONIKA spectrophotocolorimeter

MINOLTA ®, CM 260Od and after irradiation of hair with visible light in the wavelength range of 400 to 700 nanometers.

Reflectance of wicks treated with compound 1 on application and after 5 shampoos

• Reference

- Compound 1

- Compound 1 - 5 shampoos

Wavelength (nm) Reflectance of wicks treated with compound 2 on application and after 5 shampoos

2 2-5 shampoos

oooooooooooooooo

O CN - CO OO O CN - CO OO O CN - CO OO O

Wavelength (nm)

It is firstly noted that the reflectance of a lock of hair treated with a composition according to the invention is greater than that of untreated hair. The treated locks therefore appear visually clearer.

In addition, the results show that the reflectance of the locks of hair of pitch 4 treated with the compositions of the invention evolve very little after shampooing. Thus the coloration and the lightening effect on the hair remain virtually unchanged which shows a very good resistance to shampoos dyes of the invention.

Claims

1. Fluorescent dye of formula (I), (II) or (III) below:

its organic or inorganic acid salts, optical isomers, geometric isomers, and solvates such as hydrates; formulas (I), (II) or (III) in which:

> R ₃ and R ' _a , identical or different, represent an aryl (CrC ₄ ) alkyl group or a (C ₁ -C ₆ ) alkyl group optionally substituted by a hydroxyl or amino, (C ₁ -C ₄ ) alkylamino group, (C ₁ -C ₄ ) dialkylamino, said alkyl radicals being capable of forming, with the nitrogen atom carrying them, a 5- to 7-membered heterocyl, optionally comprising another heteroatom different from or different from nitrogen;

>R'c represents a hydrogen atom, an aryl (C ₁ -C ₄ ) alkyl group, an optionally substituted C-pCβ alkyl group;

> R _9, R _'g, R _"g, R" _g, R _h, R' _h, R _"h and R"_'h, identical or different, represent a hydrogen atom, a halogen atom, an amino group, (CrC ₄ ) alkylamino,

(C ₁ -C ₄ ) dialkylamino, cyano, carboxy, hydroxy, trifluoromethyl, acylamino, C ₁ -C ₄ alkoxy, (poly) hydroxyalkoxy C ₂ -C ₄ alkylcarbonyloxyalkoxycarbonyl, alkylcarbonylamino, acylamino, carbamoyl, alkylsulfonylamino, an aminosulfonyl radical, or a (C ₁ -C ₄ ) alkyl radical optionally substituted with a group chosen from (C ₁ -C ₄ ) alkoxy, hydroxy, cyano, carboxy, amino, (C ₁ -C ₄ ) alkylamino and (C ₁ -C ₄ ) dialkylamino, or the two alkyl radicals carried by the nitrogen atom of the amino group form a heterocycle comprising from 5 to 7 members and optionally comprising another heteroatom identical to or different from that of the atom nitrogen; or two groups R ₉ and R '_g; R " _g and R '"_g; R _h and R '_h; R " _h and R '" _h borne by two adjacent carbon atoms together form a benzo, indeno ring, a fused heterocycloalkyl or fused heteroaryl group; the benzo, indeno, heterocycloalkyl or heteroaryl ring being optionally substituted by a halogen atom, an amino group, (C ₁ -C ₄ ) alkylamino, (C ₁ -C ₄ ) dialkylamino, cyano, carboxy, hydroxy, trifluoromethyl, a acylamino, alkoxy, C ₁ -C ₄ (poly) hydroxyalkoxy, C ₂ -C ₄ alkoxycarbonyl alkylcarbonyloxy, alkylcarbonylamino, acylamino, carbamoyl, alkylsulfonylamino, amino-sulfonyl group, or a (C ₁ -C ₄ ) alkyl optionally substituted with: a group chosen from (C ₁ -C ₄ ) alkoxy, hydroxy, cyano, carboxy, amino, (C ₁ -C ₄ ) alkylamino, (C ₁ -C ₄ ) dialkylamino, or both radicals alkyl carried by the nitrogen atom of the amino group form a heterocycle comprising from 5 to 7 members and optionally comprising another heteroatom identical to or different from that of the nitrogen atom;

> R ₁ , R ',; R ", and R"", which may be identical or different, represent a hydrogen atom or a (C ₁ -C ₄ ) alkyl group;

R ₁ , R ₂ , R 3, R ₄ , R'-1, R ' ₂ , R ₄ and R' ₄ , which are identical or different, represent a hydrogen atom or a (C ₁ -C ₄ ) alkyl group, (C ₁ -C ₄ ) alkoxy, hydroxy, cyano, carboxy, amino, (C ₁ -C ₄ ) alkylamino, (C ₁ -C ₄ ) dialkylamino, said alkyl radicals being able to form with the nitrogen atom which carry them , a heterocycle comprising from 7-membered ring, optionally comprising another heteroatom different or different from nitrogen;

> T ₃ or T _b , identical or different, represent: i) a covalent bond σ, ii) or one or more radicals or combinations thereof selected from

-SO ₂ -, -O-, -S-, -N (R) -, -N ⁺ (R) (R ⁰ ) -, -C (O) -, with R and R °, identical or different, representing a hydrogen atom, an alkyl radical -C ₄ hydroxyalkyl, -C ₄ or aryl (Ci-C ₄₎ alkyl; iii) a heterocycloalkyl or heteroaryl radical, cationic or non-cationic, preferably monocyclic, containing one or two heteroatoms, particularly two nitrogen atoms, and in particular having from 5 to 7 members;

. identical or different, represent a grouping

cationic or non-cationic heterocyclic, optionally substituted;

> m, m ', n and n', which are identical or different, represent an integer between 0 and 6 with m + n and m '+ n', which may be identical or different, represent an integer between 1 and 10 inclusive;

> M 'representing an anionic counterion; and> Y represents: i) a hydrogen atom; ii) an alkali metal; iii) an alkaline earth metal; iv) an ammonium group: N ⁺ R ⁰¹ R ¹³ R ⁷ R ⁸ or a phosphonium group: P ⁺ R ^α R ^β R ^γ R ^δ with R ^α , R ^β , R ^γ and R ^δ , identical or different, representing a hydrogen atom or a (C ₁ -C ₄ ) alkyl group; or v) a thiol protecting group; it being understood that when the compound of formula (I), (II) or (III) contains other cationic parts, it is associated with one or more anionic counter-ions making it possible to attain the electroneutrality of formula (I ), (II) or (III).

2. Fluorescent dye of formula (I), (II) or (III) according to claim 1 wherein m, and m 'are zero.

3. Fluorescent dye of formula (I), (II) or (III) according to one of claims 1 or 2 wherein the heterocycle of formula:

i I represents a heterocyclic group or not, optionally substituted.

4. Fluorescent dye of formula (I), (II) or (III) according to one of claims 1 or 2 wherein the heterocycle of formula:

represents a heterocyclic group; monocyclic, saturated, comprising in total a single nitrogen atom and formed from 5 to 7 members.

5. Fluorescent dye of formula (III) according to any one of the preceding claims wherein Y represents a hydrogen atom, or an alkali metal.

6. Fluorescent dye of formula (III) according to any one of claims 1 to 4 wherein Y represents a protective group.

7. Fluorescent dye of formula (III) according to the preceding claim wherein Y represents a protective group selected from the following radicals: • (CrC ₄ ) alkylcarbonyl;

(C 1 -C ₄ ) alkylthiocarbonyl;

• (CrC ₄ ) alkoxycarbonyl;

• (Ci-C ₄ ) alkoxythiocarbonyl;

• (CrC ₄ ) alkylthiothiocarbonyl; (Di) (CrC ₄ ) (alkyl) aminocarbonyl;

(Di) (CrC ₄ ) (alkyl) aminothiocarbonyl;

• arylcarbonyl;

Aryloxycarbonyl;

• aryl (CrC ₄ ) alkoxycarbonyl; • (di) (C ₁ -C ₄ ) (alkyl) aminocarbonyl;

• (CrC ₄ ) (alkyl) arylaminocarbonyl;

• carboxy;

• SO3, M ⁺ with M ⁺ representing an alkali metal or M 'of the formula (III) and M ⁺ are absent; • optionally substituted aryl,

Optionally substituted heteroaryl;

. isothiouronium -C (NR ' ^c R' ^d ) = N ⁺ R ' ^e R' ^f , An ^" with R ' ^c , R' ^d , R ' ^e and R' ^f , identical or different, represent a hydrogen atom or a grouping (d C ₄ ) alkyl;

. isothiourea -C (NR ' ^c R' ^d ) = NR ' ^e with R' ^c , R ' ^d and R' ^e as defined above;

• (di) aryl (Ci-C ₄ ) optionally substituted alkyl; (Di) optionally substituted heteroaryl (CrC ₄ ) alkyl;

• CR ¹ R ² R ³ with R ¹ , R ² and R ³ identical or different, representing a halogen atom or a group selected from i) (C ₁ -C ₄ ) alkyl; ii) (C ₁ -C ₄ ) alkoxy; iii) optionally substituted aryl;

Optionally substituted heteroaryl; and • P (Z ¹ ) R ' ¹ R' ² R ' ³ with R' ¹ , and R ' ^{2 which are} identical or different, represent a hydroxyl group, (C ₁ -C ₄ ) BlCOXy or alkyl, R' ³ represents a grouping hydroxy or (C ₁ -C ₄ ) alkoxy, and Z ¹ represents an oxygen or sulfur atom;

Cyclic sterically hindered; and

Optionally substituted alkoxy (C 1 -C ₄ ) alkyl.

8. Fluorescent dye of formula (III) according to any one of the preceding claims wherein Y represents an alkali metal or a protective group chosen from:

(C _r C ₄ ) alkylcarbonyl;

>arylcarbonyl;> (CrC ₄ ) alkoxycarbonyl;

> aryloxycarbonyl;

> aryl (C 1 -C ₄ ) alkoxycarbonyl;

> (di) (C ₁ -C ₄ ) (alkyl) aminocarbonyl;

(C ₁ -C ₄ ) (alkyl) arylaminocarbonyl; optionally substituted aryl;

cationic monocyclic heteroaryl with 5 or 6 members;

8 to 11-membered cationic bicyclic heteroaryl;

cationic heterocycle of following formula:

> isothiouronium -C (NH ₂ ) = N ⁺ H ₂ , An ^" ; > isothiourea -C (NH ₂ ) = NH; and

> SO ₃ ^" , M ⁺ with M ⁺ representing an alkali metal or M 'of the formula (III) and M ⁺ are absent.

9. Fluorescent dye of formula (I), (II) or (III) according to any one of the preceding claims which comprises the ethylene group connecting the pyridinium moiety to the phenyl in ortho or para position or in positions 4-4 ', 2 -2 ', or 2-4'.

10. Fluorescent dye of formula (I) according to one of claims 1 to 4 and 9 which is symmetrical.

11. Fluorescent dye according to any one of the preceding claims, chosen from the dyes:

49

With M 'and An ^" , identical or different, representing an anionic counterion, and M ⁺ representing an alkali metal.

12. A dye composition comprising in a suitable cosmetic medium, a heterocyclic fluorescent dye of formula (I), (II) or (III) as defined in any one of claims 1 to 1 1.

13. A dye composition comprising in a suitable cosmetic medium, at least one heterocyclic fluorescent dye of formula (I), (II) or (III) as defined in any one of claims 1 to 11 and at least one reducing agent.

14. Dyeing composition according to the preceding claim wherein the reducing agent is chosen from: cysteine, homocysteine, thiolactic acid, the salts of these thiols, phosphines, bisulfite, sulfites, thioglycolic acid, as well as its esters, borohydrides and their derivatives, the sodium, lithium, potassium, calcium and quaternary ammonium salts; catecholborane.

15. Composition according to any one of claims 11 to 14, wherein the heterocyclic fluorescent dye of formula (I), (II) or (III) is present in an amount of between 0.001 and 50% by weight relative to the total weight. of the composition.

16. A method for dyeing keratin materials, in which the materials, a dye composition as defined in any one of claims 1 1 to 15, comprising in a suitable cosmetic medium, at least one heterocyclic fluorescent dye of formula (I), (II) or (III) as defined in a any of claims 1 to 11, optionally in the presence of a reducing agent capable of reducing the disulfide bonds of keratin materials.

17. The method of dyeing according to the preceding claim wherein when the heterocyclic fluorescent dye of formula (III) comprises a protective Y group, the application is preceded by a deprotection step.

18. A method of dyeing keratinous materials according to claim 16 or 17, characterized in that the keratin materials are dark keratinous fibers having a pitch of less than or equal to 6, preferably less than or equal to 4.

The method of any one of claims 16 to 18 wherein the reducing agent is applied before or after the application of the thiol fluorescent dye.

20. The method of dyeing according to any one of claims 16 to 18 wherein the fluorescent dye of formula (I) or (II) is applied at the same time as the reducer.

21. The process according to any one of claims 16 to 20, wherein the composition comprises an oxidizing agent.

22. A method according to any one of claims 16 to 20 comprising a further step of applying to the keratin fibers an oxidizing agent.

23. A multi-compartment device wherein a first compartment contains a dye composition comprising a fluorescent dye of formula (I), (II) or (III) as defined in claims 1 to 11 and a second compartment contains a reducing agent capable of to reduce the disulfide bonds of keratin materials.

24. Device according to the preceding claim comprising a third compartment which contains an oxidizing agent.

25. Use of heterocyclic thiols fluorescent dyes as defined in claims 1 to 1 1 for dyeing dark human keratin fibers.

26. Use according to the preceding claim for lightening dark keratin fibers.

27. Use according to claims 25 and 26 characterized in that the fibers keratin have a pitch of less than 6.